Note: Descriptions are shown in the official language in which they were submitted.
WO 03/029311 PCT/EP02/10446
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Rewriteable Optical Recording Material having good Solubility
The present invention relates to an optical recording material for binary
and/or multibit
and/or volume data storage, and its production and use as storage material.
It has been known for a long time that azobenzenes undergo isomerisation
processes
under the action of light [G.C. Hartley, Nature 140, 281 (1937)]. The isomeric
states
and the nature of the transition reactions between the cis and trans states
have been
investigated in various polymers that carry azobenzenes in dispersed form or
as side
chains or integrated into the main chains. [C.S. Paik; H. Morawetz,
Macromolecules
5, 171 (1972)].
It is also known that azobenzenes incorporated into polymers exhibit a
directed
orientation in an actinic light field if they are exposed to polarised light
of suitable
wavelength. Exposure to linearly polarised light leads for example to an
excess of
azobenzenes oriented perpendicularly to the direction of polarisation. This
may be
utilised to produce a light-induced double refraction in the polymer. The
orientation
mechanisms of the azobenzenes have been described many times in the
literature.
[M. Ecih; J.H. Wendorff; B. Reck; H. Ringsdorf; Makromol. Chem. Rapid Commun.
8, 59 (1987)] [Y.Q. Shen; H. Rau, Macromol. Chem. 192, 945 (1991)].
The possibility of employing such polymers for reversible optical data storage
(digital
or holographic) was described for the first time by Todorov. [T. Todorov; L.
Nikolova; N. Tomova, Appl. Opt. 23, 4309 (1984)]. There are many various types
of
materials according to the prior art for binary and/or multibit and/or volume
data
storage that contain azobenzenes as antennae for the incident light; see for
example
patent specifications EP-A 1 171 877, EP-A 1 166 187, DE-A 10 027 153, EP-A 1
166
188 and DE-A 100 271 529. Several amorphous and liquid-crystal polymers as
well as
oligomers have been synthesised and investigated in light exposure experiments
[J.J.A.
Couture; R.A. Lessard, Appl. Opt. 27, 3368 (1988)] [M. Eich; J. Wendorff, J.
Opt.
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Soc. Am. B, 7, 1428 (1990)] [A. Natansohn; P. Rochon; J. Gosselin; S. Xie;
Macromolecules 25, 2268 (1992)].
The following three factors are the basis for high light-inducible double
refraction
values of such polymers:
1. A high form anisotropy of the molecular side groups.
Form anisotropic components are termed mesogenes. Mesogenes are typically rod
shaped, due to a part of the molecule that is elongated and rigid. The length-
width
ratio measured by the van-der-Waals radii must be at least 4, preferably
between 4 and
6. The form anisotropy leads to an anisotropy of the molecular polarisability.
This
type of molecule is described in the standard literature [H. Kelker, R. Hatz,
"Handbook
of Liquid Crystals", Verlag Chemie (1980)] L. Bergmann; C. Schaefer,
"Lehrbuchfder u b
Experimentalphysik", Verlag de Gruyter, Vol. 5, "Vielteilchensysteme" (1992)].
An azo dye present in the isomeric trans state also behaves as a mesogenic
molecular
unit if it satisfies the said condition for form anisotropy.
2. A high numerical density of form anisotropic molecules, i.e. a high
azobenzene
content and/or a high mesogene content in the polymer.
3. A strongly anisotropic molecular orientation distribution. This is the
prerequisite for the molecular anisotropies (see point 1) to be manifested
macroscopically.
The degree of anisotropy may be derived from the standardised linear
absorption
dichroism A2, wherein A2 = (2A1 + All)/(3Ao), in which All and Al denote
respectively
the absorption of the polymer parallel and perpendicular to the polarisation
direction of
the actinic light and A0 denotes the absorption before the irradiation. The
absorption
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may be determined by means of a spectrometer (e.g. Varian CARY 4G, UV-/VIS
type
spectrometer).
A more general description of the molecular orientation is provided by the
order
parameter P2 = (All - A1)/(All + 2Al), wherein P2 = +1 and P2 = -0.5 represent
the
limiting values for the perfect orientation of the molecular transition dipole
moments
parallel and perpendicular to the polarisation direction of the light. P2 = 0
denotes the
isotropic case.
In particular side chain polymers, which in addition to azobenzenes also
utilise form
anisotropic components as side chains, are characterised by high light-
inducible double
refraction since they can satisfy the three prerequisites mentioned above.
In general it is true that polymers are the more sparingly soluble the better
the points 1 Y i
and 2 mentioned above are satisfied, i.e. the higher the potential is for
large double
refraction values. Dipole forces, geometric forces and entropy forces are
responsible
for this on the microscopic scale.
Many solvents, for example alcohols that are non-poisonous or are only
slightly
poisonous, are therefore not suitable as solvents. Good solvents for such
polymers are
however in many cases poisonous, carcinogenic and/or damaging to fruit. In
many
cases the volatility is also too high due to their low boiling point. An
example is
tetrahydrofuran (THF). It is described hereinafter why such solvents are
disadvantageous for the production of data storage materials, which have to
satisfy
particularly stringent ecological demands during manufacture.
In order to be able to use polymers as a function layer in a data storage
material, these
must be prepared as homogeneous films. Several casting, droplet or coating
processes
may be used for the production of thin films. A standard process used in large-
scale
production, for example of recordable compact discs ("CD-R") and their
successor
formats is spin coating. In this the dyes are dissolved and the solution is
dripped in an
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automated manner onto a rotating substrate (e.g. polycarbonate disc). After
evaporation of the solvent a thin film of the recording material remains. In
order to
trap toxicologically problematic evaporated solvent so as to protect the
environment,
the production lines for data storage materials have had to be encapsulated by
a
complicated process, which is economically disadvantageous.
It should furthermore be noted that THE dissolves polycarbonate. An imprinted
groove structure of a polycarbonate substrate would therefore be destroyed on
contact
with THF. In order to protect the groove structure a THF-resistant cover layer
had to
be applied to polycarbonate.
Reversible writing and erasing of double refraction values is a basic
prerequisite for the
use of a photo-addressable polymer as function layer in a rewriteable data
storage
material. The polymers described hitherto have the disadvantage that they do
not
sufficiently ensure the reversibility.
There was therefore a need for a recording material that exhibits light-
inducible double
refractions and that dissolves in one or more simple or modified alcohols that
are non-
poisonous or at least minimally poisonous. Furthermore the recording medium
should
exhibit a good reversibility of the exposure dynamics.
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In one aspect, the invention provides a polymeric material, the molecular
structure
of which contains a main chain and side chains, the main chain including units
derived from polyacrylate, polymethacrylate, polyacrylamide,
polymethacrylamide,
polysiloxane, polyurea, polyurethane, polyester, polystyrene or cellulose, and
the
side chains containing:
(a) at least one azobenzene dye;
(b) at least one form anisotropic grouping of the general formula (III):
(Rl1)
X3 q
(III)
z
wherein:
Z represents a radical of the general formula:
X4
(IIIa)
(R12)r
or
~
/ (R15)S (IIIb)
A
A represents 0, S or N-C1- to C4-alkyl,
X3 represents a spacer group of the general formula:
-X3,-(Q2)j-T2-S2-,
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X4 represents X4'-R13,
X3, and X4, independently of each other represent a direct bond, -0-,
-S-, -(N-R5)-, -C(R6R7)-, -(C=O)-, -(CO-O)-, -(CO-NR5)-, -(SO2)-, -(S02-O)-,
-(S02-NR5)-, -(C=NR8)- or -(CNR8-NR5)-,
R5, R8 and R13 independently of one another represent
H, Cl- to C20-alkyl, C3- to C10-cycloalkyl, C2- to C20-alkenyl, C6- to C10-
aryl,
Cl- to C20-alkyl-(C=O)-, C3- to C10-cycloalkyl-(C=O)-, C2- to C20-alkenyl-
(C=O)-,
C6- to C10-aryl-(C=O)-, Cl- to C20-alkyl-(SO2)-, C3- to C10-cycloalkyl-(SO2)-,
C2- to C20-alkenyl-(SO2)- or C6- to C10-aryl-(S02)-, or
X4'-R13 represent H, a halogen atom, cyano, nitro, CF3 or CC13,
R6 and R7 independently of each other represent H, a halogen atom,
Cl- to C20-alkyl, Cl- to C20-alkoxy, C3- to C10-cycloalkyl, C2- to C20-alkenyl
or
C6- to C10-aryl,
Y represents a single bond, -COO-, OCO-, -CONH-, -NHCO-,
-CON(CHS)-, -N(CH3)CO-, -0-, -NH- or -N(CH3)-,
R", R12, R15 independently of one another represent H, a halogen
atom, cyano, nitro, Cl- to C20-alkyl, Cl- to C20-alkoxy, phenoxy,
C3- to C10-cycloalkyl, C2- to C20-alkenyl or C6- to CIO-aryl, Cl- to C20-alkyl-
(C=O)-,
C6- to C10-aryl-(C=O)-, Cl- to C20-alkyl-(SO2)-, Cl- to C20-alkyl-(C=O)-O-,
Cl- to C20-alkyl-(C=O)-NH-, C6- to C10-aryl-(C=O)-NH-, Cl- to C20-alkyl-O-
(C=O)-,
C1- to C20-alkyl-NH-(C=O)- or C6- to C10-aryl-NH-(C=O)-,
q, r and s independently of one another are an integer of 0 to 4,
Q2 represents -0-, -S-, -(N-R5)-, -C(R6R7)-, -(C=0)-, -(CO-O)-,
-(CO-NR5)-, -(SO2)-, -(S02-O)-, -(S02-NR5)-, -(C=NR8)-, -(CNR8-NR5)-, -(CH2)p-
,
pars or meta-, C6H4- or a divalent radical of the formula:
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\/ r N/
or N
/ J
j is an integer of 0 to 4, wherein for j > 1, each Q2 may be different,
T2 represents -(CH2)p , wherein the chain is optionally interrupted by
-0-, -NR9-, or -OSiR102O-,
S2 represents a direct bond, -0-, -S-, or -NR9-,
p is an integer from 2 to 12,
R9 represents H, methyl, ethyl or propyl, and
R10 represents methyl or ethyl; and
(c) at least one monomer of the general formula:
R"
N
R R' (VI)
O
wherein:
R' and R" independently of each other represent CnH2n+1 or
CnH2n-OH, wherein n = 1 to 10, or R' and R" together represent a -CnH2n-
bridge,
wherein n= 2 to 6, a -(C2H4-0)n-C2H4-bridge, where n = 1 to 5, or a
-C2H4-N(CnH2n+1)-C2H4-bridge, wherein n = 1 to 6, and
R represents H or methyl,
wherein group (c) is contained as monomer units in the main chain.
It has surprisingly been shown that the recording materials listed in this
application
satisfy the aforementioned requirements.
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The invention accordingly provides an optical recording material that can be
used
for binary and/or multibit and/or volume data storage. The recording material
is
characterised by the fact that
= it contains at least one azobenzene dye ("azo dye"),
= it contains at least one form anisotropic grouping ("mesogene").
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Provided the azo dye has this mesogenic character, it need not contain any
further mesogene,
= it contains at least one molecular group that improves the solubility in one
or
more simple or modified alcohols, compared with the same material without
this group, the monomers of the formulae (VI) or (VIa) or hydroxyethyl group-
containing monomers, which are excellent for this purpose, being preferred,
= it optionally contains a monomer unit, preferably of the formula (V), that
is
incorporated in the polymer specifically to reduce the dye content and/or
mesogene content.
The recording material according to the invention is
$ g preferably a polymeriq( or
oligomeric organic, amorphous material, particularly preferably a side chain-
containing
polymer.
The main chains of the side chain-containing polymer are derived from the
following
basic structures: polyacrylate, polymethacrylate, polyacrylamide,
polymethacrylamide,
polysiloxane, polyurea, polyurethane, polyester, polystyrene or cellulose.
Polyacrylate,
polymethacrylate and polyacrylamide are preferred.
The main chains may contain monomer building blocks that differ from these
basic
structures. These are monomer units according to the invention of the formula
(VI).
The polymers according to the invention as a rule exist in an amorphous state
below
the clarification temperature.
The polymers and oligomers according to the invention preferably have glass
transition
temperatures Tg of at least 40 C. The glass transition temperature may be
determined
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for example according to B. Vollmer, Grundriss der Makromolekularen Chemie,
pp.
406-410, Springer-Verlag, Heidelberg 1962.
The polymers and oligomers according to the invention have a weight average
molecular weight of 5,000 to 2,000,000 g/mole, preferably 8,000 to 1,500,000
g/mole,
determined by gel permeation chromatography (calibrated with polystyrene).
In the polymers that are preferably used according to the invention azo dyes,
separated
as a rule by flexible spacers, are covalently bonded as a side chain to the
polymer main
chain. The azo dyes interact with the electromagnetic radiation and thereby
alter their
spatial orientation, with the result that double refraction can be induced in
the polymer
under the action of light and can be re-extinguished.
The mesogenes are as a rule bonded in the same way as the azo dyes. They
need4not
necessarily absorb the actinic light since they act as a passive molecular
group. They
are therefore not photoactive in the above sense. Their task is to intensify
the light-
inducible double refraction and stabilise it after the action of the light.
The molecular groups incorporated in order to improve the solubility of the
polymer
may be incorporated in three different ways:
1. As monomer units randomly integrated into the main chains. These monomer
units are not functionalised with azobenzenes or mesogenes.
2. As a side group at the bonding site between the azobenzene and spacer.
3. As a terminal group at the free end of the azo dye.
The polymers according to the invention may at the same time contain
azobenzenes
that are modified according to the descriptions 2. and 3.
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The polymers according to the invention may contain, apart from azobenzenes
that
have been modified according to the descriptions 2. and/or 3., also monomer
units
according to the description of point 1.
Azo dyes preferably have the following structure of the formula (1)
X' (R')m
(1),
(R2) X 2
wherein
R1 and R2 independently of one another denote hydrogen or a non-ionic
substituentand
m and n independently of one another denote an integer from 0 to 4, preferably
0 to 2.
X1 and X2 denote -X1,-R3 or X2'-R4,
wherein
Xl, and X2, denote a direct bond, -0-, -S-, -(N-R5)-, -C(R6R7)-, -(C=O)-, -(CO-
O)-,
-(CO-NR5)-, -(SO2)-, -(S02-O)-, -(S02-NR5)-, -(C=NR8)- or -(CNR8-NR5)-,
R3, R4, R5 and R8 independently of one another denote hydrogen, C1-C20-alkyl,
C3-C10-
cycloalkyl, C2-C20-alkenyl, C6-C10-aryl, C1-C20-alkyl-(C=O)-, C3-C10-
cycloalkyl-(C=O)-, C2-C20-alkenyl-(C=O)-, C6-C10-aryl-(C=O)-, Cl-C20-alkyl-
(SO2)-, C3-C10-cycloalkyl-(SO2)-, C2-C20-alkenyl-(SO2)- or C6-C10-aryl-(SO2)-,
or
X1.-R3 and X2'-R4 may denote hydrogen, halogen, cyano, nitro, CF3 or CC13,
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R6 and R7 independently of one another denote hydrogen, halogen, C1-C20-alkyl,
Cj-C20-alkoxy, C3-Clo-cycloalkyl, C2-C20-alkenyl or C6-Clo-aryl.
Non-ionic substituents are understood to include halogen, cyano, nitro, C1-C20-
alkyl,
C1-C20-alkoxy, phenoxy, C3-Clo-cycloalkyl, C2-C20-alkenyl or C6-Clo-aryl, C1-
C20-
alkyl-(C=O)-, C6-Cl0-aryl-(C=O)-, C1-C20-alkyl-(SO2)-, C1-C20-alkyl-(C=O)-O-,
C1-C20-alkyl-(C=O)-NH-, C6-C10-aryl-(C=O)-NH-, C1-C20-alkyl-O-(C=O)-, C1-C20-
alkyl-NH-(C=O)- or C6-C I o-aryl-NH-(C=O)-.
The alkyl, cycloalkyl, alkenyl and aryl radicals may in turn be substituted by
up to
three radicals from the group comprising halogen, cyano, nitro, C1-C20-alkyl,
C1-C20-
alkoxy, C3-Clo-cycloalkyl, C2-C20-alkenyl or C6-Clo-aryl, and the alkyl and
alkenyl
radicals may be straight chain or branched. v i
Halogen is understood to denote fluorine, chlorine, bromine and iodine, in
particular
fluorine and chlorine.
Azo dyes that possess the solubility-improving properties within the meaning
of the
invention are similarly covered by formula (I) including the abovementioned
meanings, wherein however R5 denotes C2-C1o-alkyl-OH, preferably C2-C4-alkyl-
OH,
or denotes CH2-(CH-OH)-CH2-OH.
X1 (or X2) denote a spacer group, in particular in the meaning X1'-(Q), T'-S1-
,
wherein
X" has the meaning given above,
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Q1 denotes -0-, -5-, -(N-R5)-, -C(R6R7)-, -(C=O)-, -(CO-O)-, -(CO-NR5)-, -
(SO2)-,
(S02-O)-, -(S02-NR5)-, -(C=NR8)-, -(CNR8-NR5)-, -(CH2)p , p- or m-C6H4- or
a divalent radical of the formulae
/ /
or
i denotes an integer from 0 to 4, wherein for i > 1 the individual Q1 may have
various meanings,
T1 denotes -(CH2)p , wherein the chain may be interrupted by -0-, -NR9-,
or -OSiR1020-,
S1 denotes a direct bond, -0-, -S- or -NR9-,
p denotes an integer from 2 to 12, preferably 2 to 8, in particular 2 to 4,
R9 denotes hydrogen, methyl, ethyl or propyl,
R10 denotes methyl or ethyl, and
R5 to R8 have the meanings given above.
The covalent bonding of monomers of the main chain basic structures described
above
with the azo dyes of the formula (I) via spacers yields dye monomers.
Preferred dye
monomers for polyacrylates or polymethacrylates have the formula (II)
O x
(R)m
1
R N `~.
~ x2
(R2)~
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wherein
R denotes hydrogen or methyl and
the other radicals have the meanings given above.
Particularly suitable are dye monomers of the above formula (II) wherein
X2 denotes CN, nitro and all other known electron-attracting substituents, and
R'
is preferably CN,
and the radicals R, S1, T', Q', X", and R2 as well as i, m and n have the
meanings
given above. A
Also suitable are dye monomers of the following formula (IIa)
O X (R%
VIT
R N .5~_N
(Ila),
(R2)~ X
wherein
X3 denotes hydrogen, halogen or CI-C4-alkyl, preferably hydrogen, and
the radicals R, S', T', Q', X", R1 and R2 as well as i, m and n have the
meanings given
above.
Also suitable are dye monomers of the formula (IIb)
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0 T X (R~)m
R I \ (lib),
s l / X'
(R )õ
wherein
x 4 denotes cyano or nitro, and
the radicals R, S1, T', Q', X1', R1 and R2 as well as i, m and n have the
meanings given
above.
Preferred monomer units with azo dyes that carry a solubility-improving
component at v i
the bonding site to the spacer and/or at the free position have the form:
O / N N\` N
N _ N N
rj
HO
O N~ .... N~ N
0 N.. N N
OH
OH
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OH
0 / \ N / \ N~ N\
N N OH
H
/_J
0\ -N\,
OH
HO
Mesogenic groups preferably have the structure of the formula (III)
x3 (R)q
1i (III),
Yiz
wherein Z denotes a radical of the formulae
X'4
(IIIa) or
(R,s)!
N
/ I (IIIb)
A
wherein
A denotes 0, S or N-C1-C4-alkyl,
X3 denotes a spacer group of the formula -X3'-(Q2)j-T2-S2-,
X4 denotes X4'-R13,
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X3'and X4' independently of one another denote a direct bond, -0-, -S-, -(N-
R5)-,
-C(R6R7)-, -(C=O)-, -(CO-O)-, -(CO-NR5)-, -(SO2)-, -(S02-O)-, -(S02-NR5)-,
-(C=NR8)- or -(CNR8-NR5)-,
R5, R8 and R13 independently of one another denote hydrogen, C1-C20-alkyl, C3-
C10-
cycloalkyl, C2-C20-alkenyl, C6-Clo-aryl, C1-C20-alkyl-(C=O)-, C3-C10-
cycloalkyl-(C=O)-, C2-C20-alkenyl-(C=O)-, C6-C1o-aryl-(C=O)-, C1-C20-alkyl-
(SO2)-, C3-Clo-cycloalkyl-(SO2)-, C2-C20-alkenyl-(SO2)- or C6-Clo-aryl-(SO2)-,
or
X4'-R13 may denote hydrogen, halogen, cyano, nitro, CF3 or CC13,
R6 and R7 independently of one another denote hydrogen, halogen, C1-C20-alkyl,
C1-
C20-alkoxy, CS-Clo-cycloalkyl, C2-C2o-alkenyl or C6-C10-aryl,
Y denotes a single bond, -COO-, OCO-, -CONH-, -NHCO-, -CON(CH3)-,
-N(CH3)CO-, -0-, -NH- or -N(CH3)-,
R", R12, R15 independently of one another denote hydrogen, halogen, cyano,
nitro,
C1-C20-alkyl, C1-C20-alkoxy, phenoxy, C3-C1o-cycloalkyl, C2-C20-alkenyl or
C6-C1o-aryl, C1-C20-alkyl-(C=O)-, C6-Clo-aryl-(C=O)-, C1-C20-alkyl-(SO2)-,
C1-C20-alkyl-(C=O)-O-, C1-C20-alkyl-(C=O)-NH-, C6-Clo-aryl-(C=O)-NH-,
C1-C20-alkyl-O-(C=O)-,CI-C20-alkyl-NH-(C=O)- or C6-Clo-aryl-NH-(C=O)-,
q, r and s independently of one another denote an integer from 0 to 4,
preferably 0 to 2,
Q2 denotes -0-, -S-, -(N-R5)-, -C(R6R7)-, -(C=O)-, -(CO-O)-, -(CO-NR5)-, -
(SO2)-,
-(S02-O)-, -(S02-NR5)-, -(C=NRB)-, -(CNR8-NR5)-, -(CH2)P , p- or m-C6H4- or
a divalent radical of the formulae
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N
/N J
or
j denotes an integer from 0 to 4, wherein for j > 1 the individual Q1 may have
various meanings,
T2 denotes -(CH2)p , wherein the chain may be interrupted by -0-, -NR9-,
or -OSiR102O-,
S2 denotes a direct bond, -0-, -S- or -NR9-,
p denotes an integer from 2 to 12, preferably 2 to 8, in particular 2 to 4,
R9 denotes hydrogen, methyl, ethyl or propyl, and
R10 denotes methyl or ethyl.
Preferred monomers with such form anisotropic groupings for polyacrylates or
polymethacrylates then have the formula (IV)
O T 2 /X3, (Rti1)g
S2(Q2)i (IV),
""Z
R Y
wherein
R denotes hydrogen or methyl and
the other radicals have the meanings given above.
The alkyl, cycloalkyl, alkenyl and aryl radicals may in turn be substituted by
up to
three radicals from the group comprising halogen, cyano, nitro, C1-C20-alkyl,
C1-C20-
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alkoxy, C3-Clo-cycloalkyl, C2-C20-alkenyl or C6-Clo-aryl, and the alkyl and
alkenyl
radicals may be straight chain or branched.
Halogen is understood to denote fluorine, chlorine, bromine and iodine, in
particular
fluorine and chlorine.
In the following paragraph the expression "functional building blocks" is
employed.
Functional building blocks are monomer building blocks that either contain an
azo
group or that contain a mesogenic unit. Both molecules thus designated are
involved
in the photo-orientation process of the corresponding polymer. This means that
they
are functional groups. A distinction must be made between these functional
groups or
building blocks and the "diluting building blocks". "Diluting building blocks"
are
monomer building blocks that cannot form orientatable side chains. They are
simply
part of the polymer skeleton and reduce the proportion of functional building
blocks in
the polymer.
In addition to these functional building blocks the polymers according to the
invention
may also contain building blocks that principally serve to reduce the
percentage
content of functional building blocks, in particular of dye building blocks.
Apart from
this task they may also be responsible for other properties of the polymers,
such as for
example the glass transition temperature, liquid crystallinity, film-forming
property,
etc.
For polyacrylates or polymethacrylates such monomers are acrylic acid esters
or
methacrylic acid esters of the formula (V)
R
O O Ml
R14
wherein
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R denotes hydrogen or methyl and
R14 denotes optionally branched C1-C20-alkyl or a radical containing at least
one
further acrylic unit.
Other copolymers may however also be incorporated.
The monomers units for improving the solubility have the following structure
of the
formulae (VI)-(VIa):
R"
(VI),
O
in which
R and R' either independently of one another denote CnH2n+1 or C,,H2n-OH,
where n =
1 to 10, preferably n = 1 to 3, or together denote a -C,,H2n bridge where n =
2
to 6, preferably n = 4 or 5, a -(C2H4-O)n- C2H4- bridge, where n = 1 to 5,
preferably n = 1 to 3, or a -C2H4-N(Cõ H2n+1)-C2H4- bridge where n = 1 to 6,
preferably n = 1 to 3,
where R = H or CH3,
O- R"'
R
(VIa),
wherein
R õ denotes the radical -CnH2n-OH where n = 1 to 10, preferably n = 2 to 3,
the
radical -(C2H4-O)n H where n = 2 to 4, preferably n = 2, or the radical -Cõ
H2n-
C(=O)NR R
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where n = 2 to 10, preferably n = 2 to 5, particularly preferably n = 2, where
R and R either independently of one another denote CnH2n+1 or CnH2n OH, where
n = 1 to 10, preferably n = 1 to 3, or together denote a -CnH2n- bridge where
n =
2 to 6, preferably n = 4 or 5, a -(C2H4-O)n C2H4- bridge, where n = 1 to 5,
preferably n = 1 to 3, or a -C2H4-N(Cõ H2n+1)-C2H4- bridge where n = I to 6,
preferably n = 1 to 3,
where R = H or CH3.
Polyacrylates, polymethacrylates and poly(meth)acrylates/poly(meth)acrylamides
according to the invention then preferably contain as repeating units those of
the
formula (VII), preferably those of the formulae (VII) and (VIII) or of the
formulae
(VII) and (IX), or those of the formulae (VII), (VIII) and (IX)
R
C p R
2 2C O C O
12 3. R 14
and (Q )~ X and (IX)
i (R)0
(R,)m
N Y.,Z
(R)n (V!!1)
(VI-)
x
or instead of the formula (VII) contain repeating units of the formulae (VIIa)
or (VIIb)
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R
O
2C HC O
2 S" (Q (Q)i
or
(R')m ~(R~)m
,,
(R2)n / (Vila) (R2)n (VIIb)
3
4
wherein the radicals have the meanings given above. Several of the repeating
units of
the formula (VII) and/or of the repeating units of the formulae (VIII) and/or
(IX) may
also be present. Monomer units of the formula (V) may in addition also be
presnt.
Likewise, monomer units of the formula (VI) may in addition also be present.
The quantitative ratio between V, VI, VII, VIII and IX is arbitrary.
Preferably the
concentration of VII is between 1 and 99% referred to the respective mixture.
The
ratio between VII and VIII is between 1:99 and 99:1, preferably between 10:90
and
90:10, and most particularly preferably between 60:40 and 40:60. The
proportion of V
is 0 to 90%, preferably 20 to 80%, particularly preferably 30 to 70% referred
to the
respective mixture. The proportion of VI is 0 to 90%, preferably 20 to 80%,
particularly preferably 30 to 70% referred to the respective mixture.
By means of the structure of the polymers and oligomers the intermolecular
interactions of the structural elements of the formulae (VII) with one another
or of the
formulae (VII) and (VIII) with one another are adjusted so that the formation
of liquid
crystal order states is suppressed and optically isotropic, transparent non-
scattering
films, sheets, panels or blocks, in particular films or coatings, can be
produced. On the
other hand the intermolecular interactions are still strong enough so that,
under
irradiation with light and/or under the action of static electrical fields, a
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photochemically induced, co-operative, aligned reorientation process of the
light-active
and non-light-active side groups is effected.
Preferably forces of interaction occur between the side groups of the
repeating units of
the formula (VII) and between those of the formulae (VII) and (VIII) that are
sufficient
so that the configuration change of the side groups of the formula (VII)
effects an
identically directed so-called co-operative - reorientation of the other side
groups
((VII) and/or (VIII)).
The production of the polymers and oligomers may be carried out according to
processes known in the literature, for example according to DD-A 276 297, DE-A
3 808 430, Makromolekulare Chemie 187, 1327-1334 (1984), SU-A 887 574, Europ.
Polym. 18, 561 (1982) and Liq. Cryst. 2, 195 (1987).
A further method of producing the recording material or the polymer according
to the
invention includes a process wherein at least one monomer is polymerised,
preferably
free-radical polymerised, without additional solvent, the polymerisation being
initiated
particularly preferably by free-radical starters and/or UV light and/or
thermally.
The polymerisation is carried out at temperatures between 20 C and 200 C,
preferably
between 40 C and 150 C, particularly preferably between 50 C and 100 C and
most
particularly preferably around 60 C.
In a preferred embodiment AIBN (azoisobutyronitrile) is used as free-radical
starter.
The co-use of a further, preferably liquid monomer has often proved
convenient. Such
monomers are understood to include monomers, preferably olefinically
unsaturated
monomers, particularly preferably based on acrylic acid and methacrylic acid,
and most
particularly preferably methyl methacrylate, that are liquid at the reaction
temperatures.
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Examples
Example 1: Synthesis of monomers
1.1
OH + HOv~N O~~N \ I HO^,BrO~\N \
H H O
O O
/ N HO
\ I / iN
NON \ I \ N
O~~N~ pj ~N
O J 1.1
HO
y 4~
200g of 2-anilinoethanol, 580 ml of methacrylic acid and 115.6 g of
hydroquinone and
880 ml of chloroform are refluxed while stirring. 148 ml of conc. sulfuric
acid are
slowly added dropwise. The reaction water is removed azeotropically. After
cooling,
water is added to the reaction mixture and the pH is adjusted to 6 with conc.
aqueous
soda solution. The organic phase is separated and the solvent is removed via a
rotary
evaporator. The product is purified chromatographically (silica gel; methylene
chloride). The yield of N-[2-(methacryloyloxy)ethyl] aniline is 112 g (34% of
theory).
30 g of 2-bromoethanol are added at 70 C to a reaction vessel under an argon
atmosphere. 30 g of N-[2-(methacryloyloxy)ethyl] aniline are slowly added. The
reaction mixture is then stirred for 24 hours at 100 C, and after cooling is
added to
chloroform and washed with water. After drying the reaction product with
magnesium
sulfate the chloroform is removed and the product is purified
chromatographically
(aluminium oxide; dioxane). The yield of N-(hydroxyethyl)-N-[2-
(methacryloyloxy)ethyl] aniline is 10.2 g (28%).
Elementary analysis: C14H19N03 (249.31)
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Calc.: C67.45; H7.68; N5.62;
Found: C67.30; H7.40; N5.60.
5.7 g of 4-amino-3-methyl-4'-cyanoazobenzene are added to a mixture of 40 ml
of
acetic acid and 13 ml of hydrochloric acid at 5 C, diazotised by slowly adding
8.6 g of
30% sodium nitrite solution, and coupled with 6 g of N-(hydroxyethyl)-N-[2-
(methacryloyloxy)ethyl] aniline in 200 ml of methanol at 15 C. The pH of 2.0 -
2.5 is
maintained by adding sodium acetate. The precipitate is stirred for 1 hour,
filtered off,
washed with water and methanol, dried, and filtered in dioxane through a layer
of
aluminium oxide. The yield of 1.1 is 6.2 g. M.p. 148 C.
Elementary analysis: C2sH28N603 (496.57)
Calc.: C67.73; H5.68; N16.92;
Found: C67.80; H5.70; N16.70. y l
1.2
HO Br
\ OH ii 0~.~'N
H
O
Oll '-CH
OH
ell
/ NON
~N \ I N`
O~\N \ I N'N
p 1_~OH 1.2
OH
N-(2,3-dihydroxypropyl)-N-[2-(methacryloyloxy)ethyl] aniline is produced in a
similar
manner to 1.1 from 3-bromo-1,2-propanediol and N-[2-
(methacryloyloxy)ethyl] aniline. The product is purified chromatographically
(aluminium oxide; firstly toluene/dioxane=l :1, then dioxane). The yield is
28%.
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The monomer 1.2 is produced similarly to 1.1 by diazotisation of 4-amino-3-
methyl-4 -
cyanoazobenzene and coupling with N-(2,3-dihydroxypropyl)-N-[2-(methacryl-
oyloxy)ethyl] aniline. Chromatographic purification is carried out on silica
gel in
toluene/dioxane=l:1. The yield is 30%. M.p. 148 C.
1.3
I H H
N~-~OH I ~ ~~\OH
N~ I / N~ N /
H=N / H N=N.'/
/ N"-~OH
~91 N,, N'fa "YO
TAI 1.3
0
10.7 g of 2,2-[4-(4-aminophenylazo)phenylimino]diethanol are added to a
mixture of
60 ml of water and 20 ml of hydrochloric acid at 5 C, diazotised by slowly
adding
12.8 g of 30% sodium nitrite solution, and coupled at 15 C with 10 g of N-
methyl-N-
[2-(methacryloyloxy)ethyl] aniline in 300 ml of methanol. The pH of 2.7 is
maintained
by adding sodium acetate. The precipitate is stirred for 1 hour, filtered off,
washed
with water, dried, and recrystallised from xylene. The yield of 1.3 is 7.2 g.
M.p.
149 C.
Elementary analysis: C29H34N604 (530.63)
Calc.: C65.64; H6.46; N15.84;
Found: C65.70; H6.40; N15.70.
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1.4
~H H
N N
~~OH I \ ~~~OK
\ NON ~ "`~ NON ~
H?N I N-N
~H
N\/\OH 101~(
NON II 0 =N \
O
a
N"~N O,\ N \ ' 1.4 HO
IJY
O
HO
12.8 g of 2,2-[4-(4-aminophenylazo)phenylimino]diethanol are added to a
mixture of
60 ml of water and 20 ml of hydrochloric acid at 5 C, diazotised by slowly
adding
15.2 g of 30% sodium nitrite solution, and coupled at 15 C with 10.6 g of N-
(hydroxyethyl)-N-[2-(methacryloyloxy)ethyl] aniline in 300 ml of methanol. The
pH of
2.7 is maintained by adding sodium acetate. The precipitate is stirred for 1
hour,
filtered off, washed with water, dried, and recrystallised from xylene. The
yield of 1.4
is 15 g. M.p. 105 C.
Elementary analysis: C3oH36N605 (560.66)
Calc.: C64.27; H6.47; N14.99;
Found: C64.10; H6.40; N14.20.
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Example 2a: Improvement of the solubility by the incorporation of
dimethylacrylamide
Copolymers according to the invention having the following structure are
described
hereinafter:
O N N
O~ N -9- N\
N
CH3
CH3
0.
Y
The x-monomer is functionalised with an azobenzene dye molecule. The y-monomer
consists of dimethylacrylamide (DMAA).
Five copolymers were prepared that differ as regards the monomer ratio x:y
(see
following table; identification of the polymers by consecutive numbers 1 to
5). The
copolymers are compared with the homopolymer (x = 100%; identification:
polymer
6).
The molecular weights of the polymers were determined by means of gel
permeation
chromatography (GPC). The GPC was carried out using N,N-dimethylacetamide
(DMAC) as solvent. The evaluation of the signals was carried out on the basis
of a
calibration relationship valid for PMMA at 60 C in DMAC. The values for the
weight
average molecular weight were in the range 10500 to 13300 g/mole. The values
for
the number average molecular weight were between 5500 and 6810 g/mole.
The glass transition temperatures were determined by means of heat flow
calorimetry.
Equipment: DSC-2 calorimeter from Perkin-Elmer. Two heating runs were carried
out
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from room temperature up to 300 C at a heating rate of 20 K/min. Between the
heating runs the samples were cooled rapidly at a rate of 320 K/min to room
temperature, in each case flushing with nitrogen (30 ml/min). The glass
transition
temperatures of the polymers 1 to 6 for the second heating run were between 92
and
104 C.
The solubility of the polymers was tested in various simple and modified
alcohols.
The results are shown in the following table: "+" denotes the suitable
solvents, "(+)"
denotes not completely soluble, and "-" denotes the unsuitable solvents. A 2%
solution of the polymer was used. The following solvents were investigated:
methanol, ethanol, butanol, 4-hydroxy-4-methyl-2-pentanone (HMP), 2,2,3,3-
tetrafluoropropanol (TFP) and tetrahydrofuran (THF).
Polymer Polymer Polymer Polymer Polymer Polymer
1 2 3 4 5 6
Fraction x 10 20 30 45 50 100
[mole %]
Fraction y 90 80 70 55 50 0
[mole %]
Methanol, ethanol, + - - - - -
butanol
HMP + + - - - -
TFP + + + + (+) -
THE + + + + + +
Surprisingly, a significant improvement in the solubility in TFP was achieved
by the
incorporation of DMAA; see polymer 6 compared to the polymers 1 to 5. For the
latter polymers, TFP is a suitable solvent. These polymers contain at least 50
mole %
or at least 18 wt.% of DMAA.
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Example 2b: Comparison example not according to the invention
Copolymers having the following structure are described hereinafter:
O 1
X O-1-1~N -0
N N N
N =N
O
{TJ
'.y NH2
The monomer unit x corresponds to polymer 6 (see Example 2a). The unit is
contained in an amount of 20, 30, 40 and 50 mole %. The polymers in this
sequence
are identified as polymers 2b, 3b, 4b and 5b. The monomer unit y consists of
acrylamide.
The solubility of the polymers in 2,2,3,3-tetrafluoropropanol (TFP) was tested
(20%
solution) similarly to Example 2a. The results are summarised in the following
table:
Polymer Polymer Polymer Polymer Polymer
2b 3b 4b 5b 6b
Fraction x 20 30 40 50 100
[mole %]
Fraction y 80 70 60 50 0
[mole %]
TFP + - - - -
The solubility-improving action of the monomer unit y is slight. At least 80
mole % of
the monomer unit y must be contained in the polymer for the latter to dissolve
completely in TFP. With the polymer according to the invention (see Example
2a) on
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the other hand, only 50 mole % of dimethylacrylamide (DMAA) is necessary to
achieve the same effect.
Example 3: Improvement of the solubility by using dye molecules containing
hydroxyethyl groups
Polymers were produced containing azobenzene dyes as side chains, which are
responsible for the solubility-improving action according to the invention.
The
solubility-improving hydroxyethyl groups are attached at the bonding site to
the spacer
and/or at the free position of each azobenzene dye.
The polymers produced are numbered consecutively 7 to 10:
Polymer 7:
N \ N
P N N
HO
(monomer from Example 1.1)
Polymer 8:
O N
N
01. P OH N -N
HO
(monomer from Example 1.2)
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Polymer 9:
O'_~N 0 N N~ ~ N OH
I
O
P - N N
OH
(monomer from Example 1.3)
Polymer 10:
O~~N l N OH
N 0 -N
P N wP
HO
OH
(monomer from Example 1.4)
These polymers are compared with polymer 6 (see Example 2). The result is as
follows: the polymers 7 to 10 can dissolve not only (like polymer 6) in THF,
but in
contrast to the latter also in HMP (2% concentration). The larger the
proportion of OH
groups in the polymer, the greater the forces of interaction with the hydroxy
groups of
the solvent HMP, and the better can HMP act as a solvent. The details are as
follows:
polymer 7 dissolves incompletely in HMP, polymers 8 and 9 dissolve almost
completely, and polymer 10 dissolves extremely well in HMP.
Example 4: Magnitude of the light-induced double refraction values
Several polymers according to the invention were produced which, as a thin
film,
exhibit high light-inducible double refraction values. The polymers 1 to 5
according to
the invention (see Example 2) and 7 to 10 (see Example 3) were investigated in
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illumination experiments. The magnitude of the light-induced double refraction
values
of originally isotropic polymer films was measured.
Description of the film preparation:
A 1 mm thick glass substrate is provided with a thin polymer film. The film is
applied
by means of the spin coating technique. For this, the polymer is dissolved at
a typical
concentration of 20 to 75 g/l in a suitable alcohol and the polymer solution
is applied
dropwise to the substrate rotating at a rotational speed of 2000 m. The
polymer film
that is formed typically has a thickness of 200 nm. Solvent residues are
removed from
the film by storing the coated glass support for 2 hours at 60 C in a vacuum
oven.
Description of the illumination experiment:
Each sample prepared as described above is irradiated from the polymer side
with
polarised laser light incident perpendicular thereto (writing process). An
argon ion
laser (from Continuum). at a wavelength of 514 nm serves as light source. The
intensity of this so-called writing laser is 100 mW/cm2. Trans-cis-trans-
isomerisation
cycles are induced in the azobenzene side group molecules of the polymer,
leading to a
net orientation of the side groups away from the polarisation direction of the
laser.
These molecular dynamics are manifested macroscopically in a double refraction
An in
the plane of the polymer film. The dynamics occur in the order of minutes
under the
given illumination parameters.
The time behaviour of the induced double refraction is determined
experimentally at a
wavelength of 633 nm with a helium-neon laser (typical intensity: 10 mW/cm2).
The
light of this so-called reading laser incident on the polymer layer forms a
solid angle of
15 relative to the perpendicular to the layer. The reading light and writing
light
overlap on the polymer layer. The direction of polarisation of the reading
light forms
in the plane of the polymer film an angle of 45 relative to the polarisation
of the
writing light. It is rotated on passing through the polymer layer as long as
the layer is
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double-refracting. This rotation is accompanied by an increase in the reading
light
intensity IS according to an analyser that is situated in the beam path after
the sample
and allows light perpendicular to the original polarisation direction to pass.
The
intensity Ip decreases to the same extent as IS increases. Ip is defined as
the transmitted
intensity according to a similarly positioned analyser, but which selects the
original
polarisation direction of the reading laser. Experimentally the two components
of the
polarisation direction parallel and perpendicular to the original direction
are separated
by a polarising beam splitter and are detected with the aid of two Si
photodiodes. The
double refraction An is calculated from the measured intensities by means of
the
following equation:
On = - aresin IS
7rd Is+Ip
where d denotes the thickness of the polymer layer and X = 633 nm denotes the
light
wavelength of the reading laser. In this formula it is assumed by way of
approximation
that reading takes place perpendicular to the polymer layer.
The polymers have the following double refraction values:
polymer 1: An = 0.06; polymer 2: On = 0.11; polymer 3: An = 0.17; polymer 4:
On =
0.20; polymer 5: An = 0.21; polymer 6: An = 0.44; polymer 7: An = 0.39;
polymer 8:
An = 0.10; polymer 9: An = 0.23; polymer 10: An = 0.12.
Example 5: Improvement of the reversibility of the light-induced molecular
dynamics by incorporation of dimethylacrylamide
Films of the polymers 1 to 5 according to the invention described in Example
2a were
produced according to the protocol of Example 4, illuminated for 10 minutes,
and the
double refraction structure was investigated with a reading laser. The double
refraction
An reaches its maximum value within the illumination time and maintains this
value.
An is then extinguished by rotating the polarisation direction of the writing
light by
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90 . This extinction process is complete as soon as On = 0. This first
procedure is
then directly followed by four further writing/extinction procedures according
to the
same pattern. The result is as follows: the time curve An(t) remains almost
unchanged
for each cycle. The maximum achievable double refraction values are identical
for
each cycle (permitted tolerance: 5%). The behaviour of the polymers 1 to 5 may
to a
good approximation be classed as reversible in these writing/extinction
cycles.
Fig. I shows by way of example the double refraction curve of polymer 4 during
the
five writing/extinction cycles.
The comparable experiment was already carried out beforehand with polymer 6,
which
does not contain the solubility-improving monomer unit according to the
invention.
Since the double refraction An had still not reached its maximum after 10
minutes'
illumination, the illumination time of the five writing procedures was
extended td 30
minutes. It should be noted that the shape of the double refraction curves
changes with
each new cycle. In particular, the maximum achievable double refraction value
decreases with increasing cycle number. After the end of the fifth writing
procedure
the double refraction is still only 33% of the value reached in the first
writing
procedure (see also the table hereinbelow).
Fig. 2 shows the double refraction curve of polymer 6 during the five writing/
extinction cycles.
In order to ensure that the longer illumination time compared to the polymers
1 to 5
does not qualitatively falsify the result, writing/extinction cycles were
carried out on
polymer 6 with in each case a writing time of only 100 sec. The double
refraction
curves do not reach their maximum value in this short writing time. The
results are as
follows: these cycles too do not behave reversibly, i.e. the value reached
after 100 sec.
is after the fifth cycle only 71 % of the value reached in the first cycle.
Fig. 3 shows the double refraction curve relating to this experiment:
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Summary of the results:
Polymer Polymer Polymer Polymer Polymer Polymer
1 2 3 4 5 6
Fraction x 10 20 30 45 50 100
[mole %]
Fraction y 90 80 70 55 50 0
[mole %]
Double 100 100 100 100 100 33 / 71 **
refraction value
after 5 cycles
}
* Value relative to the double refraction value of the first cycle
** 1800 sec / 100 sec writing time
By incorporating dimethacrylamide monomer units in an amount of at least 50
mole %
(see fraction y in the above table), not only was the solubility of the
polymer in TFP
achieved, but also the reversibility of the lighting dynamics was
significantly
improved. Reversible writing and extinction of double refraction values is a
basic
prerequisite for the use of a photoaddressable polymer as function layer in a
rewriteable data storage material.
Example 6: Suitability of the polymers for blue writing lasers
The example of polymer 4 shows that not only is a green writing laser suitable
(Examples 4 and 5), but for example a blue writing laser too is suitable. A
laser
illumination was performed according to the principle outlined in Example 4.
The
writing laser had a light wavelength of 407 nm and an intensity of 100 mW/cm2.
The
results are as follows: a maximum double refraction value of On = 0.2 could
likewise
be induced (measurement error ca. 10%).
